Yellow disazo dyestuffs



Patented Feb. 15, 1944 UN I T E D STAT T F F CE YELLOW DISAZO DYESTUFFS Otto Kaiser, Basel, Switzerland, assignor to the firm of Society of Basel, Switzerland Chemical Industry in Basle,

No Drawing. Application March 9, 1942, Serial 11 Claims.

in which one :1: represents an oH-group, the other a: a hydrogen atom, one y represents a SOsH-group, and the other v a hydrogen atom, in which, when the a: in the ortho-position to the N=N group represents an OH-group, that y in the para-position to this OH-group represents an SOaI-I-group, in which, also, R1 represents an aromatic nucleus of the benzene series, wherein the N=N and the groups stand in the 1:4 position to one another; further in the above formula 2. hydrogen atom is present in one position a and the indicated group H 0 H is in the other position a, and, finally, the

group represents the radical of a yellow monoa-mino azo dyestufi wherein the azo-group is united on either side to a nucleus of the benzene series. These dyestufis, the salts of whichfor example, the sodium salt-are yellow, orange, reddish or brown powders, dissolve in Water to form yellow solutions. In their neutral or weakly alkaline solutions, they possess an excellent afiinity for natural or regenerated cellulose, for example, in the form of cotton, ramie, flax, viscose or cuprammonium rayon--which may also be in the form of staple fiber or of matt rayon which has been delustered with inorganic pigments-and mixtures of these and similar fibers with one another or with animal fibers, such as Wool and silk. The dyeing process may take place in the presence or in combination with acid or mordant wool dyestuifs. On the materials named, the new dyestufis produce yellow shades which, by aftertreatment with suitable metal salts, for example, chromium, copper, cobalt, or nickel salts, may be developed, whereby the fast- 434,0il9. In Switzerland November 22, 1940 ness of the dyeings to wet agents and to light may be bettered appreciably.

These dyestuiis are most advantageously obtained if 1 molecule of the azo dyestuff of the general formula in which ac, y and R1 have the significance given above, and the one a represents a. hydrogen atom and the other a an NHz-group, be united with 1 molecule of an azo dyestuff of the general formula in which the radical has the significance already given, by treatment With phosgene to form the corresponding urea.

Among the dyestufis of the general formula already explained those which are asymmetric urea derivatives in which the mm, the yy, R1 and the ca have the meaning already given in the first paragraph of this specification, and in which the 4-(4"-amino) -benzoyl amino-l:1'-azobenzene- 3'-methoxy-4-hydroxy-3-sulfo-5-carboxylic acid, 4'-(3"-amino) -benzoylam.ino-1:1 azobenzene- 3' methyl-2-hydroxy-5-sulfo-3-carboxylic acid, 4-(3 amino) -benzoylamino-1:1-azobenzene- 2 acetylamino-'-methoxy-4-hydroxy-3-sulfo 5-carboxylic acid, 4' -(3' '-amino) -benzoylaminol:l-azobenzene-2'-methyl-5-methoxy 4 hy droxy-3-carboxy5-sulfonic acid, and so on.

In addition to the above mentioned products, their analogues .and homologues, for example, more simple compounds can be used as parent substances of the general form Rz-NHz, for example, -aminoazobenzene compounds such as 4'-amino-1 1-azobenzene-4-hydroXy-3-carboxylic acid, 4'-amino-2'-methyl-1:1'-az0benzene- 4- or 3-sulfonic acid, 4'-amino-2.-methyl-l:1'- azobenzene-4-hydroxy-3-carboxy1ic acid, 4- amino5'-methoXy-2'-methyl-l 1'-azobenzene 4-chloro-3-sulfonic acid, 4-amino-5'-methoxy- 2'-methyl-1 :1'-azobenzene-2-carboxylic acid, 4- amino-3-methoXy-4hydroxy-1 :1 azobenzene- 3-carboxylic acid, 4;-amino-3-methyl-4-hydroxyl: lf-azobenzene-3-carboxyllc acid, 2'-methoxy- 5'-amino-1 :1-azobenzene-4-hydroxy 3 carbox ylic acid, 3 methyl-5-amino-4hydroxy 1:1- azobenzene-3-carboxylic acid, etc.

The following examples illustrate the present invention without, however, limiting the scope of the same:

Example 1 6.2 parts of the monoazo dyestufl? obtained from diazotized 1-amino-4-hydroxybenzene-3- carboxy-S-sulfonic acid and l-methyl-B-amino- 4-methoxybenzene are dissolved in 500 parts of water as the sodium salt by addition of 27 parts of sodium acetate. This solution is treated at about 60 C. with 39 parts of 4-nitrobenzoyl chloride, to which has been added parts of acetone. The nitrobenzoyl product formed is reduced to the aminobenzoyl product at 65-70" C. with 34 parts of crystalline sodium sulphide, dissolved in 150 parts of water. The reduction product which separates is dissolved in 2000 parts of water by adding sodium carbonate until a definite alkaline reaction is obtained, and it is then treated for 24 hours whilst stirring at 30--40 C. with phosgene until nofree NHz-group can be detected. The urea derivative which separates out is precipitated as the sodium salt, filtered and dried. In the free state it corresponds to the formula SOaH (M3113 I HO N =N NHC OGNH OOH CH8 0 SOaH 0 on, u no N: NHC OO-NH c 0011 CH3 It is a yellow powder and dyes cotton in greenish-yellow tones fast to washing from a weakly alkaline dye bath, to which has been added a copper solution containing copper sulphate and sodium tartrate.

If the l-methyl-B-amino-d-methoxybenzene in the above example be replaced by 1-methy1-3- aminobenzene or by 1:4-dimethoxy-2-aminobenzene or 1:4-dimethyl-Z-aminobenzene, dyestufis are obtained which dye cotton in similar shades. In place of 4-nitrobenzoyl chloride, 3- nitrobenzoyl chloride or its derivatives can be used.

Example 2 70.2. parts of the monoazo dyestuff obtained from diazotized 1-amino-2-hydroxybenzene-3- carboXy-5-sulfonic acid and 1-methyl-3-aminobenzene are dissolved as the sodium salt in 500 parts of water by addition of 27 parts of sodium acetate, 39 parts of 4-nitrobenzoyl chloride, to which have been added 10 parts of acetone, are used to treat the solution at about 60 C. The nitrobenzoyl product formed is reduced with 84 parts of crystalline sodium sulfide, dissolved in parts of water, at 65-70 C. to yield the aminobenzoyl product.

The precipitated reduction product is dissolved in 2000 parts of water by addition of sodium carbonate until' a definitely alkaline reaction is obtained and is treated with phosgene for 24 hours at 30-40 C. until no free NHz-group can be detected. The urea derivative formed, which, in the free state, has the formula H O O C H C H:

is precipitated as the sodium salt, filtered and dried. It is a yellow powder and dyes cotton in reddish yellow tones fast to washing from a weakly alkaline dye bath, to which has been added a copper solution containing copper sulphate and sodium tartrate.

If the 1-methyl-3-aminobenzene is this example be replaced by 1-methyl-3-amino-4-methoxy; benzene or 1:4-dimethoxy-2-aminobenzene, dyestufis are obtained which dye rather redder shades on cotton. Similar dyestuffs are also obtained if the l-nitrobenzoyl chloride be replaced by 3-nitrobenzoyl chloride.

Example 3 38.1 parts of the -monoazo dyestuif obtained from diazotized l-aminoA-hydroxybenzene-3- carboxy-S-sulfonic acid and 1-methyl-3-aminol-methoxybenzene are dissolved in-250 parts of water as the sodium salt by addition of 13.5 parts of sodium acetate. This solution is treated at 60 C, with 18.5 parts of 4-nitrobenzoy1 chloride, to which has been added 5 parts of acetone. The nitrobenzoyl product formed is reduced with 42 parts of crystalline sodium sulphide, dissolved in '75 parts of water, at 65-'70 C. to the aminobenzoyl product.

50 parts of the isolated reduction product are dissolved in 2000 parts of water, together with 37.6 parts of 4-(4"-arnino)benzoylamino-1:lazobenzene-4-hydroXy-3-carboxylic acid, by addition of sodium carbonate until a definitely alkaline reaction is obtained, and this reaction mixture is treated with phosgen-e for 24 hours dyestufis are obtained which dye cotton in with stirring at 30-40 C. until no free NHz-group can be detected. The urea derivative is precipitated as the sodium salt, filtered and dried. The new urea corresponds to the formula SIOQH ?OH3 HO N =N-NHG OQ-NH COOH CH3 J...

It is a yellow powder and dyes cotton in greenish yellow shades fast to washing from a weakly 35.1 parts of the monoazo dyestuff derived from diazotized 1-amino-2-hydroxybenzene-3- caz-boxy-S-sulfom'c acid and l-methyl-S-aminobenzene are dissolved in the form of the sodium salt in 250 parts of water by addition of 13.5 parts of sodium acetate. This solution is treated at about 60 C. with 18.5 parts of 4-nitrobenzoyl chloride, to which have been added parts of acetone. The nitrobenzoyl product formed is reduced with 42 parts of crystalline sodium sulfide, dissolved in '75 parts of water, at 65-'70 C. to the aminobenzoyl product. 47 parts of the isolated reduction product are dissolved in 2000 parts of water, together with 27.1 parts of 4- amino-2-methyl-4'-hydroxy-1:1'-azobenzene-3'- carboxylic acid, by addition of sodium carbonate until a definitely alkaline reaction is obtained and are treated with phosgene for 24 hours at 30-40 C., with stirring, until no free NH2group can be detected. The separated urea derivative is precipitated as the sodium salt, filtered and dried. In the free state it possesses the formula I QbkNGNHC o i c H 0 0 o H l COOH CH3 Ureas of this type correspond. in the free state, to the formulae: 7

some HOONmQNHCO-QNH g o 0 on CH: l CH: V

GOOH or 03H CH: no N=NNHC OQIIIH o o o 0 on I G T=N NH coon In place of 1-methyl-3-aminobenzene, l-methyl- 3-amino-4methoxybenzene or 1:4-dimethoxy-2- aminobenzene can be used. In this way, a dyestuff possessing the formula coon OCH:

s 03H CH1 (I10 coon in the free state can be obtained.

Example 5 38.1 parts of the monoazo dyestuff obtained from diazotized 1-amino-4-hydroxybenzene-3- carboxy-B-sulfonic acid and l-methyl-S-aminol-methoxybenzene are dissolved in 250 parts of water as the sodium salt by addition of 13.5 parts of sodium acetate. This solution is treated at 60 C. with 18.5 parts of ii-nitrobenzoyl chloride, to which has been added 5 parts of acetone. The nitrobenzoyl product formed is reduced with 42 parts of crystalline sodium sulphide, dissolved in 75 parts ofwater, at 6570 C. to the aminobenzoyl product.

50 parts of the isolated reduction product are dissolved in 2000 parts of water, together with 25.7 parts of 4-amino-4'-hydroxy-1:1'-azobenzene-3'-carboxylic acid, by addition of sodium carbonate until a definitely alkaline reaction is obtained. The reaction mixture is then treated with phosgene whilst stirring at 30-40 C. until no free amino group can be detected. The separated urea derivative, which corresponds to the formula (IJOOH 03H on; lo

OOOH

If the 4-amino-4'-hydroxy-1:1 azob'enzene-3 carboxylic acid in the present example be replaced by 4 amino 2methyl-4'-hydroxy-1:1'- azobenzene-.3'-carboxylic...acid, a dyestuff is obtained which dyes cotton in similar shades.

Example 6 38.1 parts of the monoazo dyestufi derived from diazotized 1-amino-2-hydroxybenzene-3-carboxy- -sulfon'ic acid and 1-methyl-3-amino-4-methoxybenzene are dissolved in 250 parts of water as the sodium salt by addition of 13.5 parts of sodium acetate. This solution is treated at 60 C. with 18.5 parts of B-nitrobenzoyl chloride, to which has been added 5 parts of acetone. The nitrobenzoyl product formed is reduced with 42 parts of crystalline sodium sulphide, dissolved in '75 parts of water, at 65-70" C. to the aminobenzoyl product.

50 parts of the isolated reduction product are dissolved in 2000 parts of water, together with 25.7 parts of 4-amino-2-methyl-4f-hydroxy-1:1'- azobenzene-3"-carboxylic acid, by addition of sodium carbonate until a definitely alkaline reaction is obtained. The reaction mixture is then treated with phosgene whilst stirring at 40 C. until no free amino group can be detected. The separated urea derivative, which corresponds to the formula C O OH OH 0 CH3 SOaH CH3 TO C O OH OH;

Example 7 A dyebath is prepared containing 3000 parts of water, 1.4 parts of the dyestufi prepared according to Example 1, paragraph 1, and 2 parts of anhydrous sodium carbonate. 100 parts of cotton material are entered at -50" C. and the bath is heated during /2 hour to 90-95 C. 30 parts of crystalline sodium sulphate are added and-dyeing is continued at this'temperature for hour. A solution consisting of 2 p'arts'oi crystallized copper sulfate and" 2.5 parts of tartaric acid neutralized with caustic soda and made to 100 parts with water is now added to the dyebath, and the cotton is treated with this liquor for hour at 95 C. It is then rinsed and dried as usual. The cotton is dyed in a fast greenish.- yellow shade.

As indicated in the specification, the dyestufis of this application can be used on composite materials, such as materials consisting of wool-viscose rayon staple fiber. In such cases, the dyestuffs are best dyed in a neutral bath in the presence of sodium or potassium chromate. What I claim is: 1. The disazo dyestuffs which are urea derivawherein one at stands for an OH-group and the other at for a hydrogen atom, one y for a $03K- group and the other 11 for a hydrogen atom, wherein, when the :c in the o-position to the -N=N-group stands for an OI-I-group, that y in the p-position to this OH-group stands for. a SOzH-group, wherein, also, R1 stands for an aromatic nucleus of the benzene series in which the -N=N- and the I II H 0 groups stand in the 1:4-position to one another, wherein further a hydrogen atom is in one position a, and the indicated group 'l'ti H o H is in the other position a, and wherein finally the ....Iq R

group stands for the radical of a yellow monoamino azo dyestuff in which the azo-group is united on either side to a nucleus of the benzene series, which products are yellow to orange, reddish and brown powders which, in the form of their alkaline salts, dissolve in water to form yellow solutions and which dye the cellulose fiber yellow shades the fastness of which to wet agents may be improved by treatment with copper salts.

2. The disazo dyestuffs which are asymmetric urea derivatives and which, in the free state, correspond to the general formula matic nucleus of the benzene series in which the N=N-- and the groups stand in the 1:4-position to one another, wherein further a hydrogen atom is in one position a, and the indicated group N-CNR2 H (i n is in the other position a, and wherein finally the group stands for the radical of a monoaminomonoazo-dyestuff selected from the group of the 4-amino-azob'enzene compounds, which products -N=N-group stands for an OH-group, the y are yellow to orange, reddish and brown powders in the .p-position to this OH-group stands for a which, in the form of their alkaline salts, dissolve SOaH-group, wherein, also, R1 and R2 stand for n Wate 130 form y ow S u ns d Which dye an aromatic nucleus of the benzene series in the cellulose fiber yellow shades the fastness of 5 Whichthe and the which wet agents may be improved by treatment with copper salts. Tfi 3. The disazo dyestuffs which are asymmetric H urea derivatives and which, in the free state, cor- I respond to the general formula groups stand in the 1:4-position to one another, H000 z wherein one x stands for an OH-group and the and wherein finally a hydrogen atom is in one other :11 for a hydrogen atom, one 1/ for a SOsI-I- p i (land the c d group group and the other y for a hydrogen atom, wherein, when the a: in the o-position to the f R2 N N OH N=N-group stands for an OH-group, that y in H 9 H 0 OH 3;212:2 3 fg gfi gg 'fif gg gg ii gi i is in the other position a, which products are yellow to orange, reddish and brown powders an aromatlc nucleus of the benzene Senesi m which, in the form of their alkaline salts, dissolve Which the N=N and the the cellulose fiber yellow shades the fastness of which to wet agents may be improved by treat l ll ment with copper salts.

5. The disazo dyestufis which are asymmetric urea derivatives andv which, in the free state, groups stand in the 1:4-pos'ition to one another, r p n to the n r l f rm la I l z O t i a z COOH wherein further a, hydrogen atom is in one posiwherein one :1: stands for an OI-I-g'roiip and the tion a and the indicated group other a: for a hydrogen atom, one y for a $03K- group and the other 1 for a hydrogen atom, OH wherein, when the a: in the oposition to the R N R -N=N-group stands for an O-H-group, that 2/ F?? a in theip-position to this OI-I-group stands for a H o H OOOH SOaH-group, wherein, also, R1 stands for an aro- 60 matic nucleus of the benzene series in; which is in the other position a, and wherein finally R3 the and the stands for an aromatic nucleus of the benzene se- -N-o rles in Which the OI-I-group and the COOI-I-group t g stand in oosition to one another, which rodnets are ye llow to orange, reddish and b i'own Stfmd m the lA'posmon Q another powders which, in the form of their alkaline salts, 2:53 2 ifi g g af g g atom is m one p031 dissolve in water to form yellow solutions and e Ca 6 group which dye the cellulose fiber yellow shades the fastness of which to wet agents may be improved by treatment with copper salts. fi f O 4. The disazo dyestufis which are asymmetric H o n I urea derivatives and which, in the free state, cor- Z Q respond to the general formula is in theother position a and wherein finally H000 z I liI :i:N=NRiNc a f I I g -NCNRz-N=NOOH l y a g I oooH wherein one at stands for an OH-group and the one z stands for hydrogen and the other .2 for a. other a: for a hydrogen atom, one y for a SOsH- mem er of e ro p onsi i g of H and CH3, group and the other y for a hydrogen atom, which products are yellow to orange, reddish and wherein, when the a: in the o-position to the brown powde s w n the form of their alkain water to form yellow solutions and which dye line salts, dissolve group and the other y for a in water to form yellow solutions and which dye the cellulose fiber yellow shades the fastness of which to Wet agents may be improved by treatment with copper salts.

6. The disazo dyestuffs which are asymmetric urea derivatives and which, in the free state, correspond to the general formula wherein one .1: stands for an OH-group and the other a; for a hydrogen atom, one 11 for a SOzI-I- hydrogen atom, wherein, when the a: in the o-position to the -N=N-group stands for an OH-group, that y in the p-position to this OH-group stands for a SOaH-group, wherein, also, R1 stands for an aro- N=N- and the H A groups stand in the 1:4-position to one another, and whereinfinally a hydrogen atom is in one position a and the indicated group H H O H l COOH "is in the other position a, which products are yellow to orange, reddish and brown powders which,

in the form of their alkaline salts, dissolve'in water to form yellow solutions and which dye the cellulose fiber yellow shades the fastness of which to wet agents may be improved by treatment with copper salts.

7. The disazo dyestufis which are asymmetric urea derivatives and which, in the free state, correspond to the general formula OOOH wherein one 1 stands for a SOaI-I-group and the other y for a hydrogen atom, wherein, also, R1 stands for an aromatic nucleus of the benzene series, in which the N=N and the .N C I H H 0 groups stand in the 1:4-position to one another,

'matic nucleus of the benzene series in which the and wherein finally a hydrogen atom is in one position a and the indicated group 7 H t H r OOH is in the other position a, which products are yel- COOH wherein one 1/ stands for a SOzH-group and the other :11 for a hydrogen atom, wherein, also, R1 stands for an aromatic nucleus of the benzene series, carrying in ortho-position to the H A v group an O-GHz-group, and wherein further the N=N and the groups stand in the 1:4-position to one another,

and wherein finally a hydrogen atom is in one position a and the indicated group is in the other position a, which productsare yellow to orange, reddish and brown powders which, in the form of their alkaline salts, dissolve in water to form yellow solutionsand which dye the cellulose fiber yellow shades the iastness of which to wet agents may be improved by treatment with copper salts.

9, The product which, in free state, corresponds to the formula 2,341,791 10. The product which, in free state, corresponds to the formula (IJOOH 0 CH3 11. The product which, in free state, corresponds to the formula (300E OCH;

OTTO KAISER. 

